Ionic compound, coating composition comprising same, and organic light-emitting diode

ABSTRACT

The present disclosure relates to an ionic compound including an anion group of Chemical Formula 1, and a coating composition and an organic light emitting device including the same.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a national phase entry under 35 U.S.C. § 371of International Application No. PCT/KR2017/013549 filed Nov. 24, 2017,which claims priority from Korean Patent Application No. 10-2016-0158461filed Nov. 25, 2016, all of which are incorporated herein by referencein their entirety.

TECHNICAL FIELD

The present specification relates to an ionic compound, and a coatingcomposition and an organic light emitting device including the same.

BACKGROUND ART

An organic light emission phenomenon is one of examples converting acurrent to visible light by an internal process of specific organicmolecules. A principle of an organic light emission phenomenon is asfollows. When an organic material layer is placed between an anode and acathode and a current is applied between the two electrodes, electronsand holes are injected to the organic material layer from the cathodeand the anode, respectively. The holes and the electrons injected to theorganic material layer recombine to form excitons, and light emits whenthese excitons fall back to the ground state. An organic light emittingdevice using such a principle may be generally formed with a cathode, ananode, and an organic material layer placed therebetween, for example,an organic material layer including a hole injection layer, a holetransfer layer, a light emitting layer and an electron transfer layer.

Materials used in an organic light emitting device are mostly pureorganic materials or complex compounds in which organic materials andmetals form complexes, and may be divided into hole injection materials,hole transfer materials, light emitting materials, electron transfermaterials, electron injection materials and the like depending on theapplication. Herein, as the hole injection material or the hole transfermaterial, organic materials having a p-type property, that is, organicmaterials readily oxidized and having an electrochemically stable statewhen oxidized, are generally used. Meanwhile, as the electron injectionmaterial or the electron transfer material, organic materials having ann-type property, that is, organic materials readily reduced and havingan electrochemically stable state when reduced, are generally used. Asthe light emitting layer material, materials having both a p-typeproperty and an n-type property, that is, materials having a stable formin both oxidized and reduced states, are preferred, and materials havinghigh light emission efficiency converting, when excitons are formed, theexcitons to light are preferred.

In addition to the properties described above, it is preferred thatmaterials used in an organic light emitting device additionally haveproperties as follows.

First, materials used in an organic light emitting device preferablyhave excellent thermal stability. This is due to joule heating producedby charge migration in the organic light emitting device. NPB normallyused as a hole transfer layer material currently has a glass transitiontemperature of 100° C. or lower, and has a problem in that it isdifficult to use in organic light emitting devices requiring a highcurrent.

Second, in order to obtain a highly efficient organic light emittingdevice capable of low voltage driving, holes or electrons injected intothe organic light emitting device need to be smoothly transferred to alight emitting layer, and at the same time, the injected holes andelectrons need to be kept from escaping out of the light emitting layer.For this, materials used in the organic light emitting device need tohave a proper band gap and a HOMO or LUMO energy level. PEDOT:PSScurrently used as a hole transfer material in an organic light emittingdevice manufactured using a solution coating method has a lower LUMOenergy level compared to a LUMO energy level of organic materials usedas a light emitting layer material, and therefore, has a problem inmanufacturing an organic light emitting device with high efficiency andlong lifetime.

In addition thereto, materials used in an organic light emitting deviceneed to have excellent chemical stability, charge mobility, andinterface property with electrodes or adjacent layers. In other words,materials used in an organic light emitting device need to undergo lessmaterial deformation caused by moisture or oxygen. In addition, byhaving proper hole or electron mobility, the materials need to maximizeexciton formation through balancing hole and electron density in a lightemitting layer of the organic light emitting device. For devicestability, the materials also need to improve an interface withelectrodes including metals or metal oxides.

Accordingly, development of organic materials fulfilling suchrequirements has been required in the art.

DISCLOSURE Technical Problem

The present specification is directed to providing an ionic compound,and a coating composition and an organic light emitting device includingthe same.

Technical Solution

One embodiment of the present specification provides an ionic compoundincluding an anion group represented by the following Chemical Formula1.

In Chemical Formula 1,

Ar1 to Ar4 are the same as or different from each other, at least one ofAr1 to Ar4 is represented by the following Chemical Formula 2, and theremaining Ar1 to Ar4 are represented by the following Chemical Formula3,

in Chemical Formula 2, at least one of R1 to R5 is F, a cyano group, ora substituted or unsubstituted fluoroalkyl group,

at least one of the remaining R1 to R5 is a curing group,

the remaining R1 to R5 are the same as or different from each other, andeach independently hydrogen; deuterium; a nitro group; —C(O)R₁₀₀;—OR₁₀₁; —SR₁₀₂; —SO₃R₁₀₃; —COOR₁₀₄; —OC(O)R₁₀₅; —C(O)NR₁₀₆R₁₀₇; asubstituted or unsubstituted alkyl group; a substituted or unsubstitutedalkenyl group; a substituted or unsubstituted alkynyl group; asubstituted or unsubstituted amine group; a substituted or unsubstitutedaryl group; or a substituted or unsubstituted heterocyclic group,

R₁₀₀ to R₁₀₇ are the same as or different from each other, and eachindependently hydrogen; deuterium; or a substituted or unsubstitutedalkyl group,

in Chemical Formula 3, at least one of R6 to R10 is a curing group,

the remaining R6 to R10 are the same as or different from each other,and each independently hydrogen; deuterium; a nitro group; —C(O)R₁₀₀;—OR₁₀₁; —SR₁₀₂; —SO₃R₁₀₃; —COOR₁₀₄; —OC(O)R₁₀₅; —C(O)NR₁₀₆R₁₀₇; asubstituted or unsubstituted alkyl group; a substituted or unsubstitutedfluoroalkyl group; a substituted or unsubstituted alkenyl group; asubstituted or unsubstituted alkynyl group; a substituted orunsubstituted amine group; a substituted or unsubstituted aryl group; ora substituted or unsubstituted heterocyclic group, and

R₁₀₀ to R₁₀₇ are the same as or different from each other, and eachindependently hydrogen; deuterium; or a substituted or unsubstitutedalkyl group.

Another embodiment of the present specification provides a coatingcomposition including the ionic compound described above.

Still another embodiment of the present specification provides anorganic light emitting device including a first electrode; a secondelectrode; and one or more organic material layers provided between thefirst electrode and the second electrode, wherein one or more layers ofthe organic material layers include a cured material of the coatingcomposition described above.

Advantageous Effects

A compound according to one embodiment of the present specificationincludes a functional group polymerized by heat or light, and whenproviding sufficient heat or light after forming a film, tolerance to asolvent for a process is developed, and properties of the film do notchange since washing off of the compound according to one embodiment ofthe present specification or migration of interlayer materials isprevented, and as a result, an organic light emitting device havingreproducibility can be manufactured.

The compound according to one embodiment of the present specification isan ionic monomer and dissolved in a solvent coated through a solutionprocess, and then formed to a film through heat treatment or UVtreatment, and particularly, the compound according to the presentspecification can provide a low driving voltage, high light emissionefficiency and a high lifetime property when cured at around 200° C.

DESCRIPTION OF DRAWINGS

FIG. 1 illustrates an example of an organic light emitting deviceaccording to one embodiment of the present specification.

FIG. 2 shows MS data of Compound 4 according to one embodiment of thepresent specification.

FIG. 3 shows DSC data of Compound 4 according to one embodiment of thepresent specification.

FIG. 4 is an NMR spectrum of Compound 4 according to one embodiment ofthe present specification.

FIG. 5 shows DSC data of Comparative Compound 1 according to oneembodiment of the present specification Comparative.

FIG. 6 shows film retention rate data of Coating Composition 4 accordingto one embodiment of the present specification.

FIG. 7 shows film retention rate data of Coating Composition 8 accordingto one embodiment of the present specification.

FIG. 8 shows film retention rate data of Coating Composition 9 accordingto one embodiment of the present specification.

FIG. 9 is an NMR spectrum of Compound 5 according to one embodiment ofthe present specification.

REFERENCE NUMERAL

-   -   101: Substrate    -   201: Anode    -   301: Hole Injection Layer    -   401: Hole Transfer Layer    -   501: Light Emitting Layer    -   601: Electron Transfer Layer    -   701: Cathode

MODE FOR DISCLOSURE

Hereinafter, the present specification will be described in more detail.

In the present specification, a description of a certain member beingplaced “on” another member includes not only a case of the one memberadjoining the another member but a case of still another member beingpresent between the two members.

In the present specification, a description of a certain part“including” certain constituents means capable of further includingother constituents, and does not exclude other constituents unlessparticularly stated on the contrary.

Throughout the specification of the present application, the term“combination thereof” included in a Markush-type expression means amixture or a combination of one or more selected from the groupconsisting of constituents described in the Markush-type expression, andmeans including one or more selected from the group consisting of theconstituents.

One embodiment of the present specification provides a coatingcomposition including an ionic compound including an anion grouprepresented by Chemical Formula 1.

In one embodiment of the present specification, the coating compositionis for coating an organic material layer of an organic light emittingdevice.

In one embodiment of the present specification, compounds havingsolubility for proper organic solvents are preferred as the ioniccompound including the anion group represented by Chemical Formula 1.

In the present specification, a “curing group” may mean a reactivesubstituent crosslinking compounds by being exposed to heat and/orlight. The crosslinking may be produced while linking radicals producedby decomposing carbon-carbon multiple bonds or cyclic structures throughheat treatment or light irradiation.

In one embodiment of the present specification, the curing group isselected from a group of the following curing groups.

In the group of the curing groups, L is a direct bond; O; S; asubstituted or unsubstituted alkylene group; a substituted orunsubstituted arylene group; or a substituted or unsubstituted divalentheterocyclic group,

k is an integer of 1 or 2, and when k is 2, substituents in theparentheses are the same as or different from each other, and

R21 is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, various curing groupsmay be used as the curing group as long as it is a curing group capableof curing, and the curing group is not limited to the group of thecuring groups.

In the present specification, an onium compound means a compoundproduced through hydrogen ions or other organic radicals coordinatebonding to an unshared electron pair such as oxygen, sulfur, nitrogen orphosphorus.

Hereinafter, substituents of the present specification will be describedbelow in detail, however, the substituents are not limited thereto.

In the present specification,

means a site bonding to other substituents or bonding sites.

The term “substitution” in the present specification means a hydrogenatom bonding to a carbon atom of a compound is changed to anothersubstituent, and the position of substitution is not limited as long asit is a position at which the hydrogen atom is substituted, that is, aposition at which a substituent can substitute, and when two or moresubstituents substitute, the two or more substituents may be the same asor different from each other.

The term “substituted or unsubstituted” in the present specificationmeans being substituted with one or more substituents selected from thegroup consisting of hydrogen; deuterium; a halogen group; an alkylgroup; a cycloalkyl group; an alkoxy group; an aryloxy group; an arylgroup; an amine group; an arylamine group; and a curing group, or beingunsubstituted, or being substituted with a substituent linking two ormore substituents among the substituents illustrated above, or beingunsubstituted.

In the present specification, examples of the halogen group may includefluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear, branched orcyclic, and although not particularly limited thereto, the number ofcarbon atoms is preferably from 1 to 50. Specific examples thereof mayinclude methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl,isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl,n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl,1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl,2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopropyl, cyclobutyl,cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl,3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl,3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl,cyclooctyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl,2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl,1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl,5-methylhexyl and the like, but are not limited thereto.

In the present specification, the alkoxy group may be linear, branchedor cyclic. The number of carbon atoms of the alkoxy group is notparticularly limited, but is preferably from 1 to 30. Specific examplesthereof may include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy,n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy,isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy,n-octyloxy, n-nonyloxy, n-decyloxy, benxyloxy, p-methylbenxyloxy and thelike, but are not limited thereto.

The alkyl group may be substituted with an aryl group or a heterocyclicgroup to function as an arylalkyl group or a heteroarylalkyl group. Thearyl group and the heterocyclic group may be selected from amongexamples of an aryl group or a heterocyclic group to describe below.

In the present specification, the length of the alkyl group does notaffect a conjugation length of the compound, and may affect the use ofthe compound in an organic light emitting device, for example, the useof a vacuum deposition method or a solution coating method.

In the present specification, the cycloalkyl group is not particularlylimited, but preferably has 3 to 60 carbon atoms, and specific examplesthereof may include cyclopropyl, cyclobutyl, cyclopentyl,3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl,3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl,3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl,cyclooctyl and the like, but are not limited thereto.

When the aryl group is a monocyclic aryl group in the presentspecification, the number of carbon atoms is not particularly limited,but is preferably from 6 to 25. Specific examples of the monocyclic arylgroup may include a phenyl group, a biphenyl group, a terphenyl group, aquaterphenyl group and the like, but are not limited thereto.

When the aryl group is a multicyclic aryl group, the number of carbonatoms is not particularly limited, but is preferably from 10 to 30.Specific examples of the multicyclic aryl group may include a naphthylgroup, an anthracenyl group, a phenanthryl group, a pyrenyl group, aperylenyl group, a chrysenyl group, a fluorenyl group and the like, butare not limited thereto.

In the present specification, the fluorenyl group may be substituted,and adjacent substituents may bond to each other to form a ring.

When the fluorenyl group is substituted,

and the like may be included. However, the structure is not limitedthereto.

The aryl group may be substituted with an alkyl group or an alkoxy groupto function as an arylalkyl group or an aryloxy group. The alkyl groupor the alkoxy group may be selected from among the examples describedabove.

In the present specification, the number of carbon atoms of the aminegroup is not particularly limited, but is preferably from 1 to 30. Theamine group may be substituted with the above-described alkyl group,aryl group, heterocyclic group, alkenyl group, cycloalkyl group,combinations thereof, and the like, and specific examples of the aminegroup may include a methylamine group, a dimethylamine group, anethylamine group, a diethylamine group, a phenylamine group, anaphthylamine group, a biphenylamine group, an anthracenylamine group, a9-methyl-anthracenylamine group, a diphenylamine group, aphenylnaphthylamine group, a ditolylamine group, a phenyltolylaminegroup, a triphenylamine group and the like, but are not limited thereto.

In the present specification, examples of the arylamine group include asubstituted or unsubstituted monoarylamine group, a substituted orunsubstituted diarylamine group, or a substituted or unsubstitutedtriarylamine group. The aryl group in the arylamine group may be amonocyclic aryl group or a multicyclic aryl group. The arylamine groupincluding two or more aryl groups may include monocyclic aryl groups,multicyclic aryl groups, or both monocyclic aryl groups and multicyclicaryl groups. For example, the aryl group in the arylamine group may beselected from among the examples of the aryl group described above.Specific examples of the arylamine group may include phenylamine,naphthylamine, biphenylamine, anthracenylamine, 3-methyl-phenylamine,4-methyl-naphthylamine, 2-methyl-biphenylamine,9-methyl-anthracenylamine, a diphenylamine group, a phenylnaphthylaminegroup, a ditolylamine group, a phenyltolylamine group, carbazole, atriphenylamine group and the like, but are not limited thereto.

In the present specification, the heterocyclic group includes one ormore atoms that are not carbon, that is, heteroatoms, and specifically,the heteroatom may include one or more atoms selected from the groupconsisting of O, N, Se, S and the like. The number of carbon atoms isnot particularly limited, but is preferably from 2 to 30, and theheteroaryl group may be monocyclic or multicyclic. Examples of theheterocyclic group may include a thiophene group, a furanyl group, apyrrole group, an imidazolyl group, a triazolyl group, an oxazolylgroup, an oxadiazolyl group, a pyridyl group, a bipyridyl group, apyrimidyl group, a triazinyl group, a triazolyl group, an acridyl group,a pyridazinyl group, a pyrazinyl group, a quinolinyl group, aquinazolinyl group, a quinoxalinyl group, a phthalazinyl group, apyridopyrimidyl group, a pyridopyrazinyl group, a pyrazinopyrazinylgroup, an isoquinolinyl group, an indolyl group, a carbazolyl group, abenzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, abenzocarbazolyl group, a benzothiophene group, a dibenzothiophene group,a benzofuranyl group, a phenanthrolinyl group, an isoxazolyl group, athiadiazolyl group, a phenothiazinyl group, a dibenzofuranyl group andthe like, but are not limited thereto.

In the present specification, the divalent heterocyclic group means theheterocyclic group having two bonding sites, that is, a divalent group.Descriptions on the heterocyclic group provided above may be appliedthereto except for each being a divalent.

In the present specification, the arylene group means the aryl grouphaving two bonding sites, that is, a divalent group. Descriptions on thearyl group provided above may be applied thereto except for each being adivalent.

In the present specification, an “adjacent” group may mean a substituentsubstituting an atom directly linked to an atom substituted by thecorresponding substituent, a substituent sterically most closelypositioned to the corresponding substituent, or another substituentsubstituting an atom substituted by the corresponding substituent. Forexample, two substituents substituting ortho positions in a benzenering, and two substituents substituting the same carbon in an aliphaticring may be interpreted as groups “adjacent” to each other.

In the present specification, the ring formed by adjacent groups bondingto each other may be monocyclic or multicyclic, may be aliphatic,aromatic, or a fused ring of aliphatic or aromatic, and may form ahydrocarbon ring or a heteroring.

In one embodiment of the present specification, when the anion grouprepresented by Chemical Formula 1 does not have a curing group, curingdoes not occur, and device properties may decline due to migration of acation group and an anion group of the present specification betweenelectrode layers. In addition, as the number of the curing groupincreases, a coating composition curing rate increases and a filmretention rate is enhanced.

In one embodiment of the present specification, Ar1 is represented byChemical Formula 2, and Ar2 to Ar4 are represented by Chemical Formula3.

In one embodiment of the present specification, Ar1 and Ar2 arerepresented by Chemical Formula 2, and Ar3 and Ar4 are represented byChemical Formula 3.

In one embodiment of the present specification, Ar1 to Ar3 arerepresented by Chemical Formula 2, and Ar4 is represented by ChemicalFormula 3.

In one embodiment of the present specification, Ar1 to Ar4 arerepresented by Chemical Formula 2. Particularly, when Ar1 to Ar4 are allChemical Formula 2 and when a proportion of the F, the cyano group orthe fluoroalkyl group increases, a film retention rate is enhanced whenheat treating.

In one embodiment of the present specification, the ionic compoundincluding the anion group may be used in a hole injection layer of anorganic light emitting device, and, when used in the hole injectionlayer, may be used as a dopant. Herein, when the F content of the aniongroup increases, an electron attracting force from other compounds (hostcompound) increases, and holes are more favorably formed in the hostresulting in performance enhancement in the hole injection layer.

In one embodiment of the present specification, the F content may beanalyzed using a COSA AQF-100 combustion furnace coupled to a Dionex ICS2000 ion-chromatograph, or may be identified through 19F NMR, a methodgenerally used for F analysis.

In one embodiment of the present specification, Chemical Formula 2 isrepresented by any one of the following Chemical Formulae 2-1 to 2-10.

In one embodiment of the present specification, Chemical Formula 3 isrepresented by any one of the following Chemical Formulae 3-1 to 3-8.

In one embodiment of the present specification, the anion group ofChemical Formula 1 is any one selected from among the followingstructural formulae.

In the structural formulae, r is an integer of 1 to 4, q is an integerof 0 to 3, and q+r=4.

In one embodiment of the present specification, the ionic compoundincludes a cation group, and the cation group is selected from amongmonovalent cation groups, onium compounds or the following structuralformulae.

In one embodiment of the present specification, the monovalent cationgroup may be an alkali-metal cation, and the alkali-metal cation mayinclude Na⁺, Li⁺, K⁺ and the like, but is not limited thereto.

In one embodiment of the present specification, the ionic compoundincludes a cation group, and the cation group is selected from amongonium compounds or the following structural formulae.

In the structural formulae, X₁ to X₇₆ are the same as or different fromeach other, and each independently hydrogen; a cyano group; a nitrogroup; a halogen group; —COOR₁₀₄; a substituted or unsubstituted alkylgroup; a substituted or unsubstituted alkoxy group; a substituted orunsubstituted cycloalkyl group; a substituted or unsubstitutedfluoroalkyl group; or a substituted or unsubstituted aryl group, or acuring group selected from the group of the curing groups,

R₁₀₄ is hydrogen; deuterium; or a substituted or unsubstituted alkylgroup,

p is an integer of 0 to 10, and

a is 1 or 2, b is 0 or 1, and a+b=2.

In one embodiment of the present specification, the cation group isrepresented by any one of the following Chemical Formula 10 to ChemicalFormula 15.

X₁₀₀ to X₁₄₂ are the same as or different from each other, and eachindependently hydrogen; a cyano group; a nitro group; a halogen group;—COOR₁₀₄; a substituted or unsubstituted alkyl group; a substituted orunsubstituted alkoxy group; a substituted or unsubstituted cycloalkylgroup; a substituted or unsubstituted fluoroalkyl group; or asubstituted or unsubstituted aryl group, or a curing group selected fromthe group of the curing groups, and

R₁₀₄ is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, the cation group is anyone selected from among the following structural formulae.

1-1

1-2

1-3

1-4

1-5

1-6

1-7

1-8

1-9

1-10

1-11

1-12

1-13

1-14

1-15

1-16

1-17

1-18

1-19

3-1

3-2

3-3

4-1

4-2

4-3

5-1

5-2

5-3

5-4

5-5

5-6

6-1

6-2

6-3

6-4

In one embodiment of the present specification, the ionic compound isselected from among the following structural formulae.

One embodiment of the present specification provides a coatingcomposition including the ionic compound including the anion group ofChemical Formula 1.

In one embodiment of the present specification, the coating compositionincluding the ionic compound is a coating composition for an organiclight emitting device.

In one embodiment of the present specification, the coating compositionmay be a liquid phase. The “liquid phase” means in a liquid state atroom temperature and atmospheric pressure.

In one embodiment of the present specification, examples of the solventmay include chlorine-based solvents such as chloroform, methylenechloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene oro-dichlorobenzene; ether-based solvents such as tetrahydrofuran ordioxane; aromatic hydrocarbon-based solvents such as toluene, xylene,trimethylbenzene or mesitylene; aliphatic hydrocarbon-based solventssuch as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane,n-octane, n-nonane or n-decane; ketone-based solvents such as acetone,methyl ethyl ketone or cyclohexanone; ester-based solvents such as ethylacetate, butyl acetate or ethyl cellosolve acetate; polyalcohols such asethylene glycol, ethylene glycol monobutyl ether, ethylene glycolmonoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane,propylene glycol, diethoxymethane, triethylene glycol monoethyl ether,glycerin or 1,2-hexanediol, and derivatives thereof; alcohol-basedsolvents such as methanol, ethanol, propanol, isopropanol orcyclohexanol; sulfoxide-based solvents such as dimethyl sulfoxide;amide-based solvents such as N-methyl-2-pyrrolidone orN,N-dimethylformamide; benzoate-based solvents such as methyl benzoate,butyl benzoate or 3-phenoxybenzoate; tetraline, and the like, however,the solvent is not limited as long as it is a solvent capable ofdissolving or dispersing the compound according to one embodiment of thepresent disclosure.

In another embodiment, the solvent may be used either alone as one type,or as a mixture mixing two or more solvent types.

In another embodiment, the solvent preferably has a boiling point of 40°C. to 250° C., and more preferably 60° C. to 230° C., however, theboiling point is not limited thereto.

In another embodiment, the single or mixed solvent preferably hasviscosity of 1 CP to 10 CP, and more preferably 3 CP to 8 CP, however,the viscosity is not limited thereto.

In another embodiment, the coating composition preferably has aconcentration of 0.1 wt/v % to 20 wt/v %, and more preferably 0.5 wt/v %to 5 wt/v %, however, the concentration is not limited thereto.

In one embodiment of the present specification, the coating compositionmay further include one, two or more types of additives selected fromthe group consisting of thermal polymerization initiators andphotopolymerization initiators.

Examples of the thermal polymerization initiator may include peroxidessuch as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide,acetylacetone peroxide, methylcyclohexanone peroxide, cyclohexanoneperoxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide,bis-3,5,5-trimethyl hexanoyl peroxide, lauryl peroxide, benzoylperoxide, p-chlorobenzoyl peroxide, dicumyl peroxide,2,5-dimethyl-2,5-(t-butyloxy)-hexane,1,3-bis(t-butylperoxy-isopropyl)benzene, t-butyl cumyl peroxide,di-t-butyl peroxide, 2,5-dimethyl-2,5-(di-t-butylperoxy)hexane-3,tris-(t-butylperoxy)triazine,1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane,1,1-di-t-butylperoxycyclohexane, 2,2-di(t-butylperoxy)butane,4,4-di-t-butylperoxy valeric acid n-butyl ester,2,2-bis(4,4-t-butylperoxycyclohexyl)propane, t-butyl peroxyisobutyrate,di-t-butyl peroxyhexahydroterephthalate,t-butylperoxy-3,5,5-trimethylhexate, t-butyl peroxybenzoate ordi-t-butyl peroxytrimethyl adipate; or azo-based such as azobisisobutylnitrile, azobis dimethylvaleronitrile or azobis cyclohexylnitrile, but are not limited thereto.

Examples of the photopolymerization initiator may includeacetophenone-based or ketal-based photopolymerization initiators such asdiethoxyacetophenone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one,1-hydroxy-cyclohexyl-phenyl-ketone,4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1,2-hydroxy-2-methyl-1-phenylpropan-1-one,2-methyl-2-morpholino(4-methylthiophenyl)propan-1-one or1-phenyl-1,2-propanedion-2-(o-ethoxycarbonyl)oxime; benzoin ether-basedphotopolymerization initiators such as benzoin, benzoin methyl ether,benzoin ethyl ether, benzoin isobutyl ether or benzoin isopropyl ether;benzophenone-based photopolymerization initiators such as benzophenone,4-hydroxybenzophenone, 2-benzoylnaphthalene, 4-benzoylbiphenyl,4-benzoyl phenyl ether, acrylated benzophenone or 1,4-benzoylbenzene;thioxanthone-based photopolymerization initiators such as2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone,2,4-diethylthioxanthone or 2,4-dichlorothioxanthone; and, as otherphotopolymerization initiators, ethyl anthraquinone,2,4,6-trimethylbenzoyldiphenylphosphine oxide,2,4,6-trimethylbenzoylphenylethoxyphosphine oxide,bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide,bis(2,4-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide,methylphenylglyoxyester, 9,10-phenanthrene, acridine-based compounds,triazine-based compounds, imidazole-based compounds, and the like. Inaddition, those having a photopolymerization facilitating effect may beused either alone or together with the photopolymerization initiator.Examples thereof may include triethanolamine, methyldiethanolamine,ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate,(2-dimethylamino)ethyl benzoate, 4,4′-dimethylaminobenzophenone and thelike, but are not limited thereto.

Another embodiment of the present specification provides an organiclight emitting device formed using the coating composition.

In one embodiment of the present specification, the organic lightemitting device includes a first electrode; a second electrode; and oneor more organic material layers provided between the first electrode andthe second electrode, wherein one or more layers of the organic materiallayers are formed using a coating composition including an ioniccompound including the anion group of Chemical Formula 1.

In one embodiment of the present specification, the organic lightemitting device includes a first electrode; a second electrode; and oneor more organic material layers provided between the first electrode andthe second electrode, wherein one or more layers of the organic materiallayers include a cured material of a coating composition including anionic compound including the anion group of Chemical Formula 1.

In one embodiment of the present specification, the cured material ofthe coating composition is in a cured state by heat treating or lighttreating the coating composition.

In one embodiment of the present specification, the organic materiallayer including the cured material of the coating composition is a holeinjection layer.

In one embodiment of the present specification, the organic materiallayer including the cured material of the coating composition is a holeinjection layer, and the ionic compound of the cured material of thecoating composition is included as a p-doping material of the holeinjection layer.

In one embodiment of the present specification, the organic materiallayer including the cured material of the coating composition is a holeinjection layer, and the ionic compound including the anion group ofChemical Formula 1 is included as a dopant of the hole injection layer.

In one embodiment of the present specification, the organic materiallayer including the cured material of the coating composition is a holeinjection layer, and the ionic compound including the anion group ofChemical Formula 1 is included as a p-doping material of the holeinjection layer.

In the present specification, the p-doping material means a materialenabling a host material to have a p semiconductor property. The psemiconductor property means a property receiving holes throughinjection or transferring holes at a highest occupied molecular orbital(HOMO) energy level, that is, a property of a material having high holeconductivity.

In one embodiment of the present specification, the organic materiallayer formed using the coating composition is a hole injection layer,and the ionic compound including the anion group of Chemical Formula 1is a dopant of the hole injection layer, and an arylamine compound isincluded as a host of the hole injection layer.

In one embodiment of the present specification, the arylamine compoundis a monomer or a polymer.

In one embodiment of the present specification, an arylamine compoundthat is a monomer or a polymer is further included as a host of the holeinjection layer.

In one embodiment of the present specification, the arylamine compoundincludes one of the following-structured curing groups.

In the structural formulae, L is a direct bond; O; S; a substituted orunsubstituted alkylene group; a substituted or unsubstituted arylenegroup; or a substituted or unsubstituted divalent heterocyclic group,and

k is an integer of 1 or 2, and when k is 2, substituents in theparentheses are different from each other, and R21 is a substituted orunsubstituted alkyl group.

In one embodiment of the present specification, the host of the holeinjection layer has a HOMO level from 4.8 eV to 5.8 eV.

The HOMO level of the present specification is measured using anelectrochemical cyclic voltammetry method (CV). Onset potential(E_(onset)) at which host material oxidation begins is measured, andferrocene potential (E_(1/2(Fc))) is measured under the same condition.The ferrocene potential is defined as 4.8 eV with respect to a vacuumenergy level, and the HOMO level is calculated using the followingequation.HOMO(eV)=4.8+(E _(onset) −E _(1/2(Fc)))

The compound of the arylamine group forms crosslinking, and an organicmaterial layer including a thin-filmed structure is capable of beingprovided. In this case, being dissolved by a solvent deposited on asurface of the organic material layer formed using the coatingcomposition, or being morphologically influenced or decomposed may beprevented.

Accordingly, when the organic material layer formed using the coatingcomposition is formed including a step of heat treatment or lighttreatment, resistance for a solvent increases, and a multilayer may beformed by repeatedly performing solution deposition and crosslinkingmethod, and as a result, a lifetime property of a device may be enhanceddue to increased stability.

In one embodiment of the present specification, the organic materiallayer formed using the coating composition is a hole transfer layer, ahole injection layer, or a layer carrying out hole transfer and holeinjection at the same time.

In another embodiment, the organic material layer formed using thecoating composition is a light emitting layer.

In one embodiment of the present specification, the organic lightemitting device further includes one, two or more layers selected fromthe group consisting of a hole injection layer, a hole transfer layer.an electron transfer layer, an electron injection layer, an electronblocking layer and a hole blocking layer.

In one embodiment of the present specification, the first electrode is acathode, and the second electrode is an anode.

In one embodiment of the present specification, the first electrode isan anode, and the second electrode is a cathode.

In another embodiment, the organic light emitting device may be anorganic light emitting device having a structure in which an anode, oneor more organic material layers and a cathode are consecutivelylaminated on a substrate (normal type).

In another embodiment, the organic light emitting device may be anorganic light emitting device having a structure in a reverse directionin which a cathode, one or more organic material layers and an anode areconsecutively laminated on a substrate (inverted type).

The organic material layer of the organic light emitting device of thepresent specification may be formed in a single layer structure, but mayalso be formed in a multilayer structure in which two or more organicmaterial layers are laminated. For example, the organic light emittingdevice of the present disclosure may have a structure including a holeinjection layer, a hole transfer layer, a light emitting layer, anelectron transfer layer, an electron injection layer and the like as theorganic material layer. However, the structure of the organic lightemitting device is not limited thereto, and may include less numbers oforganic material layers.

For example, a structure of the organic light emitting device accordingto one embodiment of the present specification is illustrated in FIG. 1.

FIG. 1 illustrates a structure of the organic light emitting device inwhich an anode (201), a hole injection layer (301), a hole transferlayer (401), a light emitting layer (501), an electron transfer layer(601) and a cathode (701) are consecutively laminated on a substrate(101).

In FIG. 1, the hole injection layer (301), the hole transfer layer (401)and the light emitting layer (501) are formed using a coatingcomposition including the compound represented by Chemical Formula 1.

FIG. 1 illustrates the organic light emitting device, however, theorganic light emitting device is not limited thereto.

When the organic light emitting device includes a plurality of organicmaterial layers, the organic material layers may be formed withmaterials that are the same as or different from each other.

The organic light emitting device of the present specification may bemanufactured using materials and methods known in the art, except thatone or more layers of the organic material layers are formed using thecoating composition including the compound.

For example, the organic light emitting device of the presentspecification may be manufactured by consecutively laminating an anode,an organic material layer and a cathode on a substrate. Herein, theorganic light emitting device may be manufactured by forming an anode ona substrate by depositing a metal, a metal oxide having conductivity, oran alloy thereof using a physical vapor deposition (PVD) method such assputtering or e-beam evaporation, and forming an organic material layerincluding a hole injection layer, a hole transfer layer, a lightemitting layer and an electron transfer layer thereon, and thendepositing a material capable of being used as a cathode thereon. Inaddition to such a method, the organic light emitting device may also bemanufactured by consecutively depositing a cathode material, an organicmaterial layer and an anode material on a substrate.

One embodiment of the present specification also provides a method formanufacturing an organic light emitting device formed using the coatingcomposition.

Specifically, the method for manufacturing an organic light emittingdevice in one embodiment of the present specification includes preparinga substrate; forming a cathode or an anode on the substrate; forming oneor more organic material layers on the cathode or the anode; and formingan anode or a cathode on the organic material layers, wherein one ormore layers of the organic material layers are formed using the coatingcomposition.

In one embodiment of the present specification, the organic materiallayer formed using the coating composition is formed using spin coating.

In another embodiment, the organic material layer formed using thecoating composition is formed using a printing method.

In an embodiment of the present specification, examples of the printingmethod include inkjet printing, nozzle printing, offset printing,transfer printing, screen printing or the like, but are not limitedthereto.

The coating composition according to one embodiment of the presentspecification is suited for a solution process due to its structuralproperties and may be formed using a printing method, and therefore, iseconomically effective in terms of time and costs when manufacturing adevice.

In one embodiment of the present specification, the forming of anorganic material layer formed using the coating composition includescoating the coating composition on the cathode or the anode; and heattreating or light treating the coated coating composition.

In one embodiment of the present specification, the time of heattreating the organic material layer formed using the coating compositionis preferably within 1 hour and more preferably within 30 minutes.

In one embodiment of the present specification, the atmosphere of heattreating the organic material layer formed using the coating compositionis preferably inert gas such as argon or nitrogen.

In addition, the composition according to one embodiment of the presentspecification may be thin-filmed through heat treatment or lighttreatment, and may be included as a copolymer using a coatingcomposition mixed with other monomers. In addition, a copolymer or amixture may be included using a coating composition mixed with otherpolymers.

As the anode material, materials having large work function are normallypreferred so that hole injection to an organic material layer is smooth.Specific examples of the anode material capable of being used in thepresent disclosure include metals such as vanadium, chromium, copper,zinc and gold, or alloys thereof; metal oxides such as zinc oxide,indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO);combinations of metals and oxides such as ZnO:Al or SnO₂:Sb; conductivepolymers such as poly(3-methylthiophene),poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole andpolyaniline, and the like, but are not limited thereto.

As the cathode material, materials having small work function arenormally preferred so that electron injection to an organic materiallayer is smooth. Specific examples of the cathode material includemetals such as magnesium, calcium, sodium, potassium, titanium, indium,yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloysthereof; multilayer structure materials such as LiF/Al or LiO₂/Al, andthe like, but are not limited thereto.

The hole injection layer is a layer that injects holes from anelectrode, and the hole injection material is preferably a compound thathas an ability to transfer holes, therefore, has a hole injection effectin an anode, has an excellent hole injection effect for a light emittinglayer or a light emitting material, prevents excitons generated in thelight emitting layer from moving to an electron injection layer or anelectron injection material, and in addition, has an excellent thin filmforming ability. The highest occupied molecular orbital (HOMO) of thehole injection material is preferably in between the work function of ananode material and the HOMO of surrounding organic material layers.Specific examples of the hole injection material include metalporphyrins, oligothiophene, arylamine-based organic materials,hexanitrile hexaazatriphenylene-based organic materials,quinacridone-based organic materials, perylene-based organic materials,anthraquinone, and polyaniline- and polythiophene-based conductivepolymers, and the like, but are not limited thereto.

The hole transfer layer is a layer that receives holes from a holeinjection layer and transfers the holes to a light emitting layer, andas the hole transfer material, materials capable of receiving holes froman anode or a hole injection layer, moving the holes to a light emittinglayer, and having high mobility for the holes are suitable. Specificexamples thereof include arylamine-based organic materials, conductivepolymers, block copolymers having conjugated parts and non-conjugatedparts together, and the like, but are not limited thereto.

The light emitting material is a material capable of emitting light in avisible light region by receiving holes and electrons from a holetransfer layer and an electron transfer layer, respectively, and bindingthe holes and the electrons, and is preferably a material havingfavorable quantum efficiency for fluorescence or phosphorescence.Specific examples thereof include 8-hydroxyquinoline aluminum complexes(Alq₃); carbazole-based compounds; dimerized styryl compounds; BAlq;10-hydroxybenzo quinoline-metal compounds; benzoxazole-, benzthiazole-and benzimidazole-based compounds; poly(p-phenylenevinylene) (PPV)-basedpolymers; spiro compounds; polyfluorene, rubrene, and the like, but arenot limited thereto.

The light emitting layer may include a host material and a dopantmaterial. The host material includes fused aromatic ring derivatives,heteroring-containing compounds or the like. Specifically, the fusedaromatic ring derivative includes anthracene derivatives, pyrenederivatives, naphthalene derivatives, pentacene derivatives,phenanthrene compounds, fluoranthene compounds and the like, and theheteroring-containing compound includes carbazole derivatives,dibenzofuran derivatives, ladder-type furan compounds, pyrimidinederivatives and the like, however, the material is not limited thereto.

The dopant material includes aromatic amine derivatives, styrylaminecompounds, boron complexes, fluoranthene compounds, metal complexes andthe like. Specifically, the aromatic amine derivative is a fusedaromatic ring derivative having a substituted or unsubstituted arylaminogroup and includes arylamino group-including pyrene, anthracene,chrysene, peryflanthene and the like, and the styrylamine compound is acompound in which substituted or unsubstituted arylamine is substitutedwith at least one arylvinyl group, and one, two or more substituentsselected from the group consisting of an aryl group, a silyl group, analkyl group, a cycloalkyl group and an arylamino group are substitutedor unsubstituted. Specifically, styrylamine, styryldiamine,styryltriamine, styryltetramine or the like is included, however, thestyrylamine compound is not limited thereto. In addition, the metalcomplex includes iridium complexes, platinum complexes or the like, butis not limited thereto.

The electron transfer layer is a layer that receives electrons from anelectron injection layer and transfers the electrons to a light emittinglayer, and as the electron transfer material, materials capable offavorably receiving electrons from a cathode, moving the electrons to alight emitting layer, and having high mobility for the electrons aresuitable. Specific examples thereof include Al complexes of8-hydroxyquinoline; complexes including Alq₃; organic radical compounds;hydroxyflavon-metal complexes, and the like, but are not limitedthereto. The electron transfer layer may be used together with anydesired cathode material as used in the art. Particularly, examples ofthe suitable cathode material include common materials that have smallwork function, and in which an aluminum layer or a silver layer follows.Specifically, the cathode material includes cesium, barium, calcium,ytterbium and samarium, and in each case, an aluminum layer or a silverlayer follows.

The electron injection layer is a layer that injects electrons from anelectrode, and the electron injection material is preferably a compoundthat has an ability to transfer electrons, has an electron injectioneffect from a cathode, has an excellent electron injection effect for alight emitting layer or a light emitting material, prevents excitonsgenerated in the light emitting layer from moving to a hole injectionlayer, and in addition, has an excellent thin film forming ability.Specific examples thereof include fluorenone, anthraquinodimethane,diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole,imidazole, perylene tetracarboxylic acid, fluorenylidene methane,anthrone or the like, and derivatives thereof, metal complex compounds,nitrogen-containing 5-membered ring derivatives, and the like, but arenot limited there.

The metal complex compound includes 8-hydroxyquinolinato lithium,bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper,bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum,tris(2-methyl-8-hydroxyquinolinato)aluminum,tris(8-hydroxyquinolinato)gallium,bis(10-hydroxybenzo[h]quinolinato)berylium,bis(10-hydroxybenzo[h]quinolinato)zinc,bis(2-methyl-8-quinolinato)chlorogallium,bis(2-methyl-8-quinolinato)(o-cresolato)gallium,bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum,bis(2-methyl-8-quinolinato)(2-naphtholato)gallium and the like, but isnot limited thereto.

The hole blocking layer is a layer blocking holes from reaching acathode, and generally, may be formed under the same condition as thehole injection layer. Specifically, oxadiazole derivatives or triazolederivatives, phenanthroline derivatives, BCP, aluminum complexes and thelike are included, however, the material is not limited thereto.

The organic light emitting device according to the present specificationmay be a top-emission type, a bottom-emission type or a dual-emissiontype depending on the materials used.

In one embodiment of the present specification, the coating compositionmay be included in organic solar cells or organic transistors inaddition to organic light emitting devices.

Hereinafter, the present specification will be described in detail withreference to examples in order to specifically describe the presentspecification. However, the examples according to the presentspecification may be modified to various different forms, and the scopeof the present specification is not to be construed as being limited tothe examples described below. Examples of the present specification areprovided in order to more fully describe the present specification tothose having average knowledge in the art.

EXAMPLE Preparation Example 1 Preparation of Compound 1

Mg (95 mg, 3.9214 mmol), THF (10 mL) and I₂ (4 mg) were placed in a 25mL round bottom flask, and stirred.1-Bromo-2,3,5,6-tetrafluoro-4-(1,2,2-trifluorovinyl)benzene (1.2 g,3.9214 mmol) was introduced to the reaction solution, and the result wasstirred at room temperature. After 10 hours, dissolution of Mg wasidentified by the solution becoming black, and ether (10 mL) and BCl₃(1.3 mL, 1.3 mmol, 1 M in hexane solution) were added thereto over 30minutes. After stirring the reaction solution for a day, Na₂CO₃ (30 mL,3.0 mmol, 0.1 M in H₂O) was added thereto. The synthesized material wasextracted using EA (3×10 mL), and then residual water was removed withMgSO₄. After removing all the solvent, water was completely removed withDean-stark using benzene, and the solids were filtered to obtain atarget compound (430 mg). (Yield: 35%)

Sodiumtetrakis(2,3,5,6-tetrafluoro-4-(1,2,2-trifluorovinyl)phenyl)borate (300mg, 0.3158 mmol), diphenyliodonium chloride (100 mg, 0.3158 mmol), H₂O(10 mL) and acetone (10 mL) were placed in a 25 mL round bottom flask,and vigorously stirred for 30 minutes. The result was extracted usingdichloromethane (10 mL×3), and then dried after removing the solvent toobtain a target compound (381 mg). (Yield: 100%)

Preparation Example 2 Preparation of Compound 2

Methyltriphenyl potassium bromide (16 g, 45.2489 mmol) andtetrahydrofuran (THF) (100 mL) were placed in a 250 mL round bottomflask, and stirred for 30 minutes at 0° C. n-BuLi (18.1 mL, 45.2489mmol, 2.5 M in hexane) was slowly added to the reaction solution, andthe result was stirred for 30 minutes at 0° C. At 0° C.,4-bromo-2,6-difluorobenzaldehyde (5.0 g, 22.6244 mmol, in 30 mLtetrahydrofuran (THF)) was slowly added to the reaction solution. Thereaction solution was stirred while slowly raising the temperature toroom temperature. After 3 hours, ether (100 mL) and a saturated NH₄Clsolution (400 mL) were added to the reaction solution. The organicsolvent was extracted using ether (2×200 mL), and residual water wasremoved with MgSO₄. The result was columned using EA:Hex=1:9 to obtain atarget compound (3 g). (Yield: 60%)

Mg (111 mg, 4.5656 mmol), THF (10 mL) and I₂ (4 mg) were placed in a 25mL round bottom flask, and stirred. 5-Bromo-1,3-difluoro-2-vinylbenzene(1 g, 4.5656 mmol) was introduced to the reaction solution, and theresult was stirred at room temperature. After 10 hours, dissolution ofMg was identified by the solution becoming black, and ether (10 mL) andBCl₃ (1.1 mL, 1.0957 mmol, 1 M in hexane solution) were added theretoover 30 minutes. After stirring the reaction solution for a day, Na₂CO₃(30 mL, 3.0 mmol, 0.1 M in H₂O) was added thereto. The synthesizedmaterial was extracted using EA (3×10 mL), and residual water wasremoved with MgSO₄. After removing all the solvent, water was completelyremoved with Dean-stark using benzene, and the solids were filtered toobtain a target compound (400 mg). (Yield: 62%)

Sodium tetrakis(3,5-difluoro-4-vinylphenyl)borate (400 mg, 0.6776 mmol),diphenyliodonium chloride (215 mg, 0.6776 mmol), H₂O (10 mL) and acetone(10 mL) were placed in a 25 mL round bottom flask, and vigorouslystirred for 30 minutes. The result was extracted using dichloromethane(10 mL×3), and then dried after removing the solvent to obtain a targetcompound (574 mg). (Yield: 100%)

Preparation Example 3 Preparation of Compound 3

Methyltriphenyl potassium bromide (13.90 g, 38.9135 mmol) andtetrahydrofuran (THF) (100 mL) were placed in a 250 mL round bottomflask, and stirred for 30 minutes at 0° C. n-BuLi (15.6 mL, 38.9135mmol, 2.5 M in hexane) was slowly added to the reaction solution, andthe result was stirred for 30 minutes at 0° C. At 0° C.,4-formyl-2,3,5,6-tetrafluoro-1-bromobenzene (5.0 g, 19.4568 mmol, in 30mL tetrahydrofuran (THF)) was slowly added to the reaction solution. Thereaction solution was stirred while slowly raising the temperature toroom temperature. After 3 hours, ether (100 mL) and a saturated NH₄Clsolution (400 mL) were added to the reaction solution. The organicsolvent was extracted using ether (2×200 mL), and residual water wasremoved with MgSO₄. The result was columned using EA:Hex=1:9 to obtain atarget compound (1.29 g). (Yield: 26%)

Mg (95 mg, 3.9214 mmol), THF (10 mL) and I₂ (4 mg) were placed in a 25mL round bottom flask, and stirred.1-Bromo-2,3,5,6-tetrafluoro-4-vinylbenzene (1.0 g, 3.9214 mmol) wasintroduced to the reaction solution, and the result was stirred at roomtemperature. After 10 hours, dissolution of Mg was identified by thesolution becoming black, and ether (10 mL) and BCl₃ (1.3 mL, 1.3 mmol, 1M in hexane solution) were added thereto over 30 minutes. After stirringthe reaction solution for a day, Na₂CO₃ (30 mL, 3.0 mmol, 0.1 M in H₂O)was added thereto. The synthesized material was extracted using EA (3×10mL), and residual water was removed with MgSO₄. After removing all thesolvent, water was completely removed with Dean-stark using benzene, andthe solids were filtered to obtain a target compound (340 mg). (Yield:28%)

Sodium tetrakis (2,3,5,6-tetrafluoro-4-vinylphenyl)borate (200 mg,0.2724 mmol), 1-(4-vinylbenzyl)pyridin-1-ium chloride (69 mg, 0.2996mmol), H₂O (10 mL) and MC (10 mL) were placed in a 25 mL round bottomflask, and vigorously stirred for 30 minutes. The organic solvent wasextracted using ether (3×10 mL), and residual water was removed withMgSO₄. The solvent was removed, and the result was vacuum dried toobtain Compound 3 (247 mg). (Yield: 100%)

Preparation Example 4 Preparation of Compound 4

Sodium tetrakis(2,3,5,6-tetrafluoro-4-(perfluorocyclopropyl)phenyl)borate (501 mg,0.6823 mmol), diphenyliodonium chloride (216 mg, 0.6823 mmol), H₂O (10mL) and acetone (10 mL) were placed in a 25 mL round bottom flask, andvigorously stirred for 30 minutes. When precipitates were produced, theprecipitates were washed with water to obtain target Compound 4 (677mg). (Yield: 100%)

MS data of Compound 4 are shown in FIG. 2, DSC data of Compound 4 areshown in FIG. 3, and an NMR spectrum of Compound 4 is shown in FIG. 4.

The DSC data are differential scanning calorimeter data, and curing ofthe dopant material was seen through FIG. 3.

Preparation Example 5 Preparation of Compound 5

Potassium carbonate (10.4 g, 75.3 mmol) and then dimethylformamide (DMF)(200 ml) were placed in a 500 mL round bottom flask. To the flask,2,3,5,6-tetrafluorophenol (10.0 g, 60.22 mmol) was introduced, and theresult was stirred for 30 minutes at 60° C. 4-Vinylbenzyl chloride (7.66g, 50.18 mmol) was slowly added to the reaction solution, and the resultwas stirred for 16 hours at 60° C. After that, H₂O (300 mL) and EA (200ml) were added. The organic layer was extracted using EA (2×200 mL), andresidual water was removed with MgSO₄. The result was columned usingEA:Hex=1:9 to obtain a target compound (11.2 g). (Yield: 79%)

After placing 1,2,4,5-tetrafluoro-3-((4-vinylbenzyl)oxy)benzene (10 g,35.43 mmol) in a 250 ml round bottom flask, ether (130 ml) wasintroduced thereto, and the result was stirred. The reaction solutionwas cooled to −78° C., and stirred for 30 minutes. n-BuLi (17 ml, 42.52mmol, 2.5 M in hexane) was slowly injected thereto over 30 minutes.After that, the result was stirred for 1 hour. BCl₃ (8.15 ml, 8.15 mmol,1 M in hexane) was slowly introduced thereto over 30 minutes. Afterthat, the result was further stirred for 2 hours, and the temperature ofthe reaction solution was slowly raised to room temperature. Afterstirring the reaction solution for a day, H₂O (200 ml) was addedthereto. The synthesized material was extracted using ether (3×100 mL),and all the solvent was removed. After that, water was completelyremoved with Dean-stark using benzene, and the solids were filtered toobtain a target compound (6.2 g). (Yield: 66%)

Lithium tetrakis(2,3,5,6-tetrafluoro-4-((4-vinylbenzyl)oxy)phenyl)borate (6.2 g, 5.42mmol), diphenyliodonium chloride (2.57 g, 8.13 mmol), H₂O (50 mL) andacetone (10 mL) were placed in a 25 mL round bottom flask, andvigorously stirred for 30 minutes. The organic solvent was extractedusing MC (3×20 mL), and the solvent was removed. The result was columnedusing MC:acetone=9:1 to obtain target Compound 7 (5.0 g). (Yield: 65%)

[FIG. 9]: NMR Spectrum of Compound 5

Preparation Example 6 Preparation of Compound 6

1-Bromo-2,3,5,6-tetrafluoro-4-(1,2,2-trifluorovinyl)benzene (3 g, 9.7093mmol) and hexafluoropropylene oxide (3 g, 18.0701 mmol) were placed in a15 mL stainless steel cylinder, and heated for 4 hours at 190° C. Afterslowly cooling the container, the solution inside the container waswashed 3 times with water (5 mL). The organic solution was dried usingmagnesium sulfate. This mixture was silica column purified using a 9:1hexane:ethyl acetate solvent to obtain a target compound (1.2 g).(Yield: 34%)

Mg (81 mg, 3.3427 mmol), THF (10 mL) and I₂ (4 mg) were placed in a 25mL round bottom flask, and stirred.1-Bromo-2,3,5,6-tetrafluoro-4-(perfluorocyclopropyl)benzene (1.2 g,3.3427 mmol) was introduced to the reaction solution, and the result wasstirred at room temperature. After 10 hours, complete dissolution of Mgwas identified by the solution becoming black, and ether (10 mL) andBCl₃ (0.8 mL, 0.8022 mmol, 1 M in heptane solution) were added theretoover 30 minutes. After stirring the reaction solution for a day, Na₂CO₃(30 mL, 3.0 mmol, 0.1 M in H₂O) was added thereto. The synthesizedmaterial was extracted using EA (3×10 mL), and then residual water wasremoved with MgSO₄. After removing all the solvent, water was completelyremoved with Dean-stark using benzene, and the solids were filtered toobtain a target compound (410 mg). (Yield: 44%)

Sodiumtetrakis(2,3,5,6-tetrafluoro-4-(perfluorocyclopropyl)phenyl)borate (410mg, 0.3565 mmol), diphenyliodonium chloride (113 mg, 0.3565 mmol), H₂O(10 mL) and acetone (10 mL) were placed in a 25 mL round bottom flask,and vigorously stirred for 30 minutes. The result was extracted usingdichloromethane (10 mL×3) and then dried after removing the solvent toobtain a target Compound 6 (502 mg). (Yield: 100%)

Preparation Example 7 Preparation of Compound 7

(4-Bromo-2,6-bis(trifluoromethyl)phenyl)methanol (4 g, 12.3828 mmol),phosphorus pentoxide (290 mg, 3.7148 mmol) and hydroquinone (82 mg,0.7430 mmol) were placed in a 25 mL round bottom flask, and stirred for1 hour at 160° C. After cooling the reaction solution to roomtemperature, a saturated aqueous sodium bicarbonate solution (15 mL) wasslowly added thereto. The synthesized material was extracted using MC(3×10 mL), and residual water was removed with MgSO₄. After removing theMC solvent, the result was purified using silica gel columnchromatography (10% ethyl acetate/hexane), and dried to obtain a targetcompound (2.6 g). (Yield: 65%)

Mg (198 mg, 8.1494 mmol), THF (20 mL) and I₂ (8 mg) were placed in a 100mL round bottom flask, and stirred.5-Bromo-1,3-bis(trifluoromethyl)-2-vinylbenzene (2.6 g, 8.1494 mmol) wasintroduced to the reaction solution, and the result was stirred at roomtemperature. After 10 hours, dissolution of Mg was identified by thesolution becoming black, and ether (20 mL) and BCl₃ (2.0 mL, 1.9559mmol, 1 M in hexane solution) were added thereto over 30 minutes. Afterstirring the reaction solution for a day, Na₂CO₃ (40 mL, 3.0 mmol, 0.1 Min H₂O) was added thereto. The synthesized material was extracted usingEA (3×20 mL), and residual water was removed with MgSO₄. After removingall the solvent, water was completely removed with Dean-stark usingbenzene, and the solids were filtered to obtain a target compound (1.1g). (Yield: 59%)

Sodium tetrakis(3,5-bis(trifluoromethyl)-4-vinylphenyl)borate (2 g,2.0195 mmol), diphenyliodonium chloride (639 mg, 2.0195 mmol), H₂O (20mL) and acetone (20 mL) were placed in a 50 mL round bottom flask, andvigorously stirred for 30 minutes. The result was extracted usingdichloromethane (20 mL×3), and then dried after removing the solvent toobtain target Compound 7 (2.5 g). (Yield: 100%)

Experimental Example 1-1 Formation of Coating Layer Using CoatingComposition

The coating composition was mixed as described in the following Table 1,and specifically, Coating Composition 1 was produced by mixing ap-doping material represented by the following Compound 1, a hostcompound that is the following [Compound A], and an organic solvent(cyclohexanone). Specifically, Compound 1, Compound A and the organicsolvent were mixed in a weight ratio of 2:8:490 to produce the coatingcomposition, and Coating Composition 1 was spin coated to form a coatinglayer, and the film was baked at 250° C. or lower.

Coating Composition 2 was produced in the same manner as CoatingComposition 1 except that the following Compound 2 was used instead ofCompound 1 of the present disclosure. Coating Composition 2 was spincoated to form a coating layer, and the film was baked at 250° C. orlower.

Coating Composition 3 was produced in the same manner as CoatingComposition 1 except that the following Compound 3 was used instead ofCompound 1 of the present disclosure. Coating Composition 3 was spincoated to form a coating layer, and the film was baked at 250° C. orlower.

Coating Composition 4 was produced in the same manner as CoatingComposition 1 except that the following Compound 4 was used instead ofCompound 1 of the present disclosure. Coating Composition 4 was spincoated to form a coating layer, and the film was baked at 250° C. orlower.

Coating Composition 5 was produced in the same manner as CoatingComposition 4 except that the following [Compound B] was used instead of[Compound A] of the present disclosure. Coating Composition 5 was spincoated to form a coating layer, and the film was baked at 250° C. orlower.

Coating Composition 6 was produced in the same manner as CoatingComposition 4 except that the following [Compound C] was used instead of[Compound A] of the present disclosure. Coating Composition 6 was spincoated to form a coating layer, and the film was baked at 250° C. orlower.

Coating Composition 7 was produced in the same manner as CoatingComposition 1 except that the following Compound 7 was used instead ofCompound 1 of the present disclosure. Coating Composition 7 was spincoated to form a coating layer, and the film was baked at 250° C. orlower.

Coating Composition 8 was produced in the same manner as CoatingComposition 1 except that the following Comparative Compound 1 was usedinstead of Compound 1 of the present disclosure. Coating Composition 8was spin coated to form a coating layer, and the film was baked at 250°C. or lower.

Coating Composition 9 was produced in the same manner as CoatingComposition 1 except that the following Comparative Compound 2 was usedinstead of Compound 1 of the present disclosure. Coating Composition 9was spin coated to form a coating layer, and the film was baked at 250°C. or lower.

Experimental Example 1-2 Experiments on Film Retention Rate of CoatingLayer

In order to check the film retention rate of the coating layer formedusing each of Coating Compositions 4, 8 and 9, a toluene solvent wasspin treated on the top of the film, and the result was washed.

Specifically, Coating Composition 4 was spin coated for 60 seconds at aspin rate of 1000 rpm, and then baked through heating for 30 minutes ona hot plate at 230° C. to form a thin film. The result was immersed for10 minutes in toluene, taken out, and the film retention rate wasmeasured using UV-Visible spectroscopy and shown in FIG. 6.

FIG. 6 shows film retention rate data of Coating Composition 4.

The film retention rate was measured in the same manner except thatCoating Composition 8 was used instead of Coating Composition 4, andshown in FIG. 7. FIG. 7 shows film retention rate data of CoatingComposition 8.

The film retention rate was measured in the same manner except thatCoating Composition 9 was used instead of Coating Composition 4, andshown in FIG. 8. FIG. 8 shows film retention rate data of CoatingComposition 9.

The film retention rate data were obtained by comparing the degree ofultraviolet absorbance before and after the process of forming the filmdescribed above.

Through the above-mentioned results, it was seen that the result of FIG.6 and the film retention rate data of FIG. 7 and FIG. 8 had a differencein the absorbance, and it means having a difference in the film-formingeffect due to the difference in the absorbance. Accordingly, it wasidentified that Coating Composition 4 had increased chemical resistanceand film retention rate compared to Coating Compositions 8 and 9.

TABLE 1 Baking Spin Rate Temperature Coating p-Doping (rpm)/Time (°C.)/Time Composition Host Material (s) (min) 1 Compound A Compound 11000/60 230/30 2 Compound A Compound 2 1000/60 230/30 3 Compound ACompound 3 1000/60 230/30 4 Compound A Compound 4 1000/60 230/30 5Compound B Compound 4 1000/60 230/30 6 Compound C Compound 4 1000/60230/30 7 Compound A Compound 7 1000/60 230/30 8 Compound A Comparative1000/60 230/30 Compound 1 9 Compound A Comparative 1000/60 230/30Compound 2

Example 1

A glass substrate on which indium tin oxide (ITO) was deposited as athin film to a thickness of 1,500 Å was placed in detergent-dissolveddistilled water and ultrasonic cleaned. After the ITO was cleaned for 30minutes, ultrasonic cleaning was repeated twice using distilled waterfor 10 minutes. After the cleaning with distilled water was finished,the substrate was ultrasonic cleaned with solvents of isopropyl alcoholand acetone for 30 minutes each, dried, and then transferred to a glovebox.

On the transparent ITO electrode prepared as above, Coating Composition1 described in the table was spin coated to form a hole injection layerhaving a thickness of 300 Å, and the coating composition was cured for30 minutes on a hot plate under N₂ atmosphere. After that, the resultwas transferred to a vacuum depositor, and then Compound D was vacuumdeposited on the hole injection layer to form a hole transfer layer.

Subsequently, a light emitting layer was formed on the hole transferlayer by vacuum depositing Compound F in a concentration of 8% withrespect to Compound E to a thickness of 300 Å. On the light emittinglayer, Compound G was vacuum deposited to a thickness of 200 Å to forman electron injection and transfer layer. A cathode was formed on theelectron injection and transfer layer by depositing LiF to a thicknessof 12 Å and aluminum to a thickness of 2,000 Å in consecutive order.

In the above-mentioned processes, the deposition rates of the organicmaterials were maintained at 0.4 Å/sec to 0.7 Å/sec, the depositionrates of the LiF and the aluminum of the cathode were maintained at 0.3Å/sec and 2 Å/sec, respectively, and the degree of vacuum during thedeposition was maintained at 2×10⁻⁷ to 5×10⁻⁸ torr.

Example 2

An organic light emitting device was manufactured in the same manner asin Example 1 except that Coating Composition 2 was used instead ofCoating Composition 1 as the hole injection layer.

Example 3

An organic light emitting device was manufactured in the same manner asin Example 1 except that Coating Composition 3 was used instead ofCoating Composition 1 as the hole injection layer.

Example 4

An organic light emitting device was manufactured in the same manner asin Example 1 except that Coating Composition 4 was used instead ofCoating Composition 1 as the hole injection layer.

Example 5

An organic light emitting device was manufactured in the same manner asin Example 1 except that Coating Composition 5 was used instead ofCoating Composition 1 as the hole injection layer.

Example 6

An organic light emitting device was manufactured in the same manner asin Example 1 except that Coating Composition 6 was used instead ofCoating Composition 1 as the hole injection layer.

Example 7

An organic light emitting device was manufactured in the same manner asin Example 1 except that Coating Composition 7 was used instead ofCoating Composition 1 as the hole injection layer.

Comparative Example 1

An organic light emitting device was manufactured in the same manner asin Example 1 except that Coating Composition 8 was used instead ofCoating Composition 1 as the hole injection layer.

Comparative Example 2

An organic light emitting device was manufactured in the same manner asin Example 1 except that Coating Composition 9 was used instead ofCoating Composition 1 as the hole injection layer.

Results of measuring driving voltage and light emission efficiency forthe organic light emitting devices manufactured using theabove-described method at current density of 10 mA/cm² are shown in thefollowing Table 2.

TABLE 2 Driving Current Power Voltage Efficiency Efficiency LifetimeExample (V) (cd/A) (lm/W) (95%, h) Example 1 5.20 7.02 4.24 37 Example 23.60 6.40 5.58 41 Example 3 5.80 7.70 4.17 80 Example 4 4.70 7.69 5.1439 Example 5 4.80 7.74 5.06 40 Example 6 4.40 7.34 5.24 43 Example 74.20 6.77 5.06 32 Comparative 9.70 11.96 3.87 1 Example 1 Comparative4.30 6.60 4.82 20 Example 2

Based on the results of Table 2, it was identified that the dopanthaving the structure of Chemical Formula 1 of the present specificationhad superior solubility for an organic solvent compared togenerally-used dopants, and was thereby suited for solution processes,and, since a coating composition was readily prepared, a uniform coatinglayer may be formed using the coating composition. In addition, unlikeexisting dopants, a curing group was present preventing a lifetimedecrease caused by interlayer inflow, and therefore, the dopant was ableto be used in an organic light emitting device.

The invention claimed is:
 1. An ionic compound comprising an anion grouprepresented by the following Chemical Formula 1:

wherein, in Chemical Formula 1, Ar1 to Ar4 are the same as or differentfrom each other, at least one of Ar1 to Ar4 is represented by thefollowing Chemical Formula 2, and the remaining Ar1 to Ar4 if presentare represented by the following Chemical Formula 3,

in Chemical Formula 2, at least one of R1 to R5 is F, a cyano group, ora substituted or unsubstituted fluoroalkyl group; at least one of theremaining R1 to R5 is a curing group; the remaining R1 to R5 if presentare the same as or different from each other, and each independentlyhydrogen; deuterium; a nitro group; —C(O)R₁₀₀; —OR₁₀₁; —SR₁₀₂; —SO₃R₁₀₃;—COOR₁₀₄; —OC(O)R₁₀₅; —C(O)NR₁₀₆R₁₀₇; a substituted or unsubstitutedalkyl group; a substituted or unsubstituted alkenyl group; a substitutedor unsubstituted alkynyl group; a substituted or unsubstituted aminegroup; a substituted or unsubstituted aryl group; or a substituted orunsubstituted heterocyclic group; R₁₀₀ to R₁₀₇ are the same as ordifferent from each other, and each independently hydrogen; deuterium;or a substituted or unsubstituted alkyl group,

in Chemical Formula 3, at least one of R6 to R10 is a curing group; theremaining R6 to R10 if present are the same as or different from eachother, and each independently hydrogen; deuterium; a nitro group;—C(O)R₁₀₀; —OR₁₀₁; —SR₁₀₂; —SO₃R₁₀₃; —COOR₁₀₄; —OC(O)R₁₀₅;—C(O)NR₁₀₆R₁₀₇; a substituted or unsubstituted alkyl group; asubstituted or unsubstituted fluoroalkyl group; a substituted orunsubstituted alkenyl group; a substituted or unsubstituted alkynylgroup; a substituted or unsubstituted amine group; a substituted orunsubstituted aryl group; or a substituted or unsubstituted heterocyclicgroup; and R₁₀₀ to R₁₀₇ are the same as or different from each other,and each independently hydrogen; deuterium; or a substituted orunsubstituted alkyl group, wherein the curing group is selected from thegroup consisting of the following curing groups:

wherein, L is a direct bond; O; S; a substituted or unsubstitutedalkylene group; a substituted or unsubstituted arylene group; or asubstituted or unsubstituted divalent heterocyclic group, provided thatthe arylene group is not a phenyl group, k is an integer of 1 or 2, andwhen k is 2, the Ls are the same as or different from each other; andR21 is a substituted or unsubstituted alkyl group.
 2. The ionic compoundof claim 1, wherein Chemical Formula 2 is represented by any one of thefollowing Chemical Formulae 2-1 to 2-10:


3. The ionic compound of claim 1, wherein Chemical Formula 3 isrepresented by any one of the following Chemical Formulae 3-1 to 3-8:


4. The ionic compound of claim 1, wherein the anion group of ChemicalFormula 1 is any one selected from among the following structuralformulae:

in the structural formulae, r is an integer of 1 to 4, q is an integerof 0 to 3, and q+r=4.
 5. The ionic compound of claim 1, furthercomprising a cation group, wherein the cation group is selected fromamong monovalent cation groups, onium compounds or the followingstructural formulae:

in the structural formulae, X₁ to X₇₅ are the same as or different fromeach other, and each independently hydrogen; a cyano group; a nitrogroup; a halogen group; —COOR₁₀₄; a substituted or unsubstituted alkylgroup; a substituted or unsubstituted alkoxy group; a substituted orunsubstituted cycloalkyl group; a substituted or unsubstitutedfluoroalkyl group; or a substituted or unsubstituted aryl group, or acuring group; R₁₀₄ is hydrogen; deuterium; a substituted orunsubstituted alkyl group; p is an integer of 0 to 10; and a is 1 or 2,b is 0 or 1, and a+b=2.
 6. The ionic compound of claim 5, wherein thecation group is represented by any one of the following Chemical Formula10 to Chemical Formula 15:

X₄₇ to X₅₀, X₁₀₀ to X₁₂₉ and X₁₃₃ to X₁₄₂ are the same as or differentfrom each other, and each independently hydrogen; a cyano group; a nitrogroup; a halogen group; —COOR₁₀₄; a substituted or unsubstituted alkylgroup; a substituted or unsubstituted alkoxy group; a substituted orunsubstituted cycloalkyl group; a substituted or unsubstitutedfluoroalkyl group; or a substituted or unsubstituted aryl group, or acuring group; and R₁₀₄ is a substituted or unsubstituted alkyl group. 7.The ionic compound of claim 5, wherein the cation group is any oneselected from among the following structural formulae:


8. The ionic compound of claim 1, which is selected from among thefollowing structural formulae:


9. A coating composition comprising the ionic compound of claim
 1. 10.The coating composition of claim 9, which is for an organic lightemitting device.
 11. The coating composition of claim 9, furthercomprising an arylamine compound that is a monomer or a polymer.
 12. Thecoating composition of claim 11, wherein the arylamine compound includesat least one of the following-structured curing groups:

in the structural formulae, L is a direct bond; O; S; a substituted orunsubstituted alkylene group; a substituted or unsubstituted arylenegroup; or a substituted or unsubstituted divalent heterocyclic group;and k is an integer of 1 or 2, and when k is 2, the Ls are differentfrom each other, and R21 is a substituted or unsubstituted alkyl group.13. An organic light emitting device comprising: a first electrode; asecond electrode provided opposite to the first electrode; and one ormore organic material layers provided between the first electrode andthe second electrode, wherein one or more layers of the organic materiallayers include a cured material of the coating composition of claim 9.14. The organic light emitting device of claim 13, wherein the curedmaterial of the coating composition is in a cured state by heat treatingor light treating the coating composition.
 15. The organic lightemitting device of claim 13, wherein the organic material layerincluding the cured material of the coating composition is a holetransfer layer, a hole injection layer, or a layer carrying out holetransfer and hole injection at the same time.
 16. The organic lightemitting device of claim 13, wherein the organic material layerincluding the cured material of the coating composition is a holetransfer layer, and the ionic compound of the cured material of thecoating composition is included as a p-doping material of the holeinjection layer.
 17. The organic light emitting device of claim 16,further comprising an arylamine compound that is a monomer or a polymeras a host of the hole injection layer.
 18. The organic light emittingdevice of claim 17, wherein the arylamine compound includes at least oneof the following-structured curing groups:

in the structural formulae, L is a direct bond; O; S; a substituted orunsubstituted alkylene group; a substituted or unsubstituted arylenegroup; or a substituted or unsubstituted divalent heterocyclic group;and k is an integer of 1 or 2, and when k is 2, the Ls are differentfrom each other, and R21 is a substituted or unsubstituted alkyl group.19. The organic light emitting device of claim 16, wherein a host of thehole injection layer is a compound having a HOMO level from 4.8 eV to5.8 eV.